EP3264504A1 - Particules de matériau actif enrobées de polyimide, suspension épaisse pour matériau d'électrode, électrode négative, batterie, et procédé de fabrication de particules de matériau actif enrobées de polyimide - Google Patents

Particules de matériau actif enrobées de polyimide, suspension épaisse pour matériau d'électrode, électrode négative, batterie, et procédé de fabrication de particules de matériau actif enrobées de polyimide Download PDF

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EP3264504A1
EP3264504A1 EP16755290.0A EP16755290A EP3264504A1 EP 3264504 A1 EP3264504 A1 EP 3264504A1 EP 16755290 A EP16755290 A EP 16755290A EP 3264504 A1 EP3264504 A1 EP 3264504A1
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Prior art keywords
active material
polyimide
negative electrode
coated
battery
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EP16755290.0A
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German (de)
English (en)
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EP3264504B1 (fr
EP3264504A4 (fr
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Kae Fujiwara
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IST Corp Japan
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IST Corp Japan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polyimide-coated active material particle, a slurry for an electrode material, an electrode (for example, a negative electrode), and a battery.
  • the present invention also relates to a method for producing polyimide-coated active material particle.
  • a negative electrode constituting a lithium secondary battery includes active material particles alloyed with lithium, such as silicon particles.
  • the active material particles alloyed with lithium repeatedly expand and shrink following repeated occlusion and release of lithium ions caused by charging and discharging.
  • a problem caused by the repeated expansion and shrinkage of the active material particles is that active material particles themselves and a binder contained in the active material layer are fractured and a charge-discharge cycle characteristic is deteriorated.
  • the present invention provides an electrode material (active material particles, slurry, etc.) which can suppress the amount of organic solvent used and improve the charge-discharge cycle of the electrode.
  • a polyimide-coated active material particle according to the present invention includes an active material particle and a polyimide layer derived from a monomeric polyimide precursor and coated on the active material particle.
  • the thickness of the polyimide layer in the polyimide-coated active material particle may be 0.5 nm or more and 50 nm or less.
  • the polyimide layer in the polyimide-coated active material particle may have a porous structure.
  • the polyimide layer in the polyimide-coated active material particle may further include a polyimide resin derived from a polymeric polyimide precursor.
  • a slurry for an electrode material according to the present invention includes the above-described polyimide-coated active material particle of the present invention and an aqueous binder.
  • the aqueous binder in the slurry for an electrode material may be a polyacrylic acid, a styrene-butadiene rubber, carboxymethyl cellulose, or a mixture of at least two thereof.
  • the slurry for an electrode material may further include an electrically conductive additive.
  • a negative electrode according to the present invention includes a current collector and an active material layer including the above-described polyimide-coated active material particle of the present invention and an aqueous binder.
  • a negative electrode according to another aspect of the present invention includes a current collector and an active material layer formed by applying the above-described slurry for an electrode material of the present invention to the current collector.
  • a battery according to the present invention includes a positive electrode, the above-described negative electrode of the present invention, a separator disposed between the positive electrode and the negative electrode, and an electrolyte-containing medium filled between the positive electrode and the negative electrode.
  • a battery according to another aspect of the present invention includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte-containing medium filled between the positive electrode and the negative electrode, wherein the negative electrode includes a current collector and an active material layer including negative electrode active material particles and an aqueous binder, and a ratio of a charge-discharge cycle characteristic of the battery to a charge-discharge cycle characteristic of a battery including a negative electrode having an active material layer using a polyimide as a binder is 43.0% or more.
  • a method for producing a polyimide-coated active material particle according to the present invention includes a coating step of coating an active material particle with a polyimide precursor solution including a monomeric polyimide precursor, and a heating step of heating the active material particle coated with the monomeric polyimide precursor.
  • a slurry for an electrode material of a battery including active material particles coated with a polyimide layer derived from a monomeric polyimide precursor and an aqueous binder.
  • the slurry for an electrode material of the present invention it is possible to form a negative electrode in which the degree of deterioration of charge-discharge cycle characteristic is suppressed to a low level without using an organic solvent having a large environmental load as a binder. Therefore, it is possible to reduce the amount of organic solvent used in the electrode production process.
  • heating at a high temperature is required to convert a polyimide precursor into a polyimide.
  • aqueous binder is used and a polyimide binder is not used, it is not necessary to perform high-temperature treatment in the electrode production process. Therefore, it is not necessary to use a high-temperature furnace or an environment equipment that prevents a copper foil, which is a collector, from oxidation, and increase in equipment cost can be suppressed.
  • the active material layer of the negative electrode constituting the battery includes the negative electrode active material particles coated with the polyimide layer derived from the monomeric polyimide precursor, and the aqueous binder.
  • a negative electrode produced using polyimide-coated active material particles and a battery equipped with the negative electrode will be described as specific examples of the present invention.
  • an example of the slurry for an electrode material of the present invention which is used for producing an electrode such as a negative electrode will also be described.
  • a method for producing active material particles coated with a polyimide will be described.
  • Fig. 1 shows the cross-sectional configuration of the negative electrode according to an embodiment of the present invention.
  • a negative electrode 200 according to an embodiment of the present invention includes an active material layer 20 and a current collector 30.
  • the negative electrode 200 is suitable for a lithium secondary battery or the like.
  • the active material layer 20 is formed on the current collector 30.
  • the active material layer 20 and the current collector 30 will be described hereinbelow in detail.
  • the active material layer 20 has polyimide-coated active material particles 21 and an aqueous binder 22.
  • the thickness of the active material layer 20 can be, for example, within the range of 10 ⁇ m or more and 100 ⁇ m or less. However, in the present invention, this thickness is not particularly limited.
  • Each polyimide-coated active material particle 21 is mainly formed from an active material particle 23 and a polyimide layer 24 derived from a monomeric polyimide precursor and coated on the active material particle 23.
  • the polyimide-coated active material particle 21 is an example of the polyimide-coated active material particle of the present invention.
  • aqueous binder 22 it is particularly preferable to use polyacrylic acid, styrene-butadiene rubber, carboxymethyl cellulose, or a mixture of at least two of them as the aqueous binder 22.
  • polyacrylic acid styrene-butadiene rubber, carboxymethyl cellulose, or a mixture of at least two of them
  • aqueous binder 22 By using such an aqueous binder, it is possible to obtain a more satisfactory binding property of the polyimide-coated active material particles.
  • the amount of the aqueous binder 22 in the active material layer 20 is preferably 1% by mass or more and 50% by mass or less, more preferably 1.5% by mass or more and 35% by mass or less, and even more preferably 2% by mass or more and 25% by mass or less of the total mass of the active material layer 20.
  • the amount of the aqueous binder is 1% by mass or more and 50% by mass or less, the adhesion between the active material particles and between the active material particles and the current collector is strong and a high cycle characteristic can be maintained.
  • the aqueous binder 22 may include an electrically conductive additive.
  • An electrically conductive filler is an example of the electrically conductive additive.
  • Examples of the electrically conductive filler include carbon black, Ketjen black, acetylene black, carbon whiskers, carbon fibers such as vapor-grown carbon fibers (VGCF), natural graphite, artificial graphite, carbon nanoparticles, carbon nanotubes, metal powders or metal fibers including titanium oxide, ruthenium oxide, aluminum, nickel, copper or the like, and electrically conductive oxides and nitrides. These conductive fillers may be used singly or in combination.
  • the active material layer 20 can be formed from a slurry for an electrode material. Details of the slurry for an electrode material will be described below.
  • the current collector 30 is preferably an electrically conductive metal foil.
  • the electrically conductive metal foil is formed of a metal such as copper, nickel, iron, titanium, and cobalt, or an alloy such as stainless steel obtained by combining these metals.
  • the surface of the current collector 30 may be roughened in order to improve binding property with the active material layer 20.
  • the surface roughening of the current collector 30 is performed by providing electrolytic copper or an electrolytic copper alloy on the surface of the current collector 30.
  • polyimide-coated active material particles 21 contained in the slurry for an electrode material and a method for producing the same will be described.
  • the polyimide-coated active material particle 21 is mainly composed of the active material particle 23 and the polyimide layer 24 coated on the active material particle 23.
  • the average particle diameter of the active material particles 23 is more than 0 ⁇ m and less than 20 ⁇ m, preferably more than 0 ⁇ m and less than 10 ⁇ m, even more preferably more than 0 ⁇ m and less than 8 ⁇ m, still more preferably more than 0 ⁇ m and less than 7 ⁇ m, and most preferably more than 0 ⁇ m and less than 6 ⁇ m.
  • the average particle diameter as referred to herein, is measured by a laser diffraction/scattering method using a particle diameter distribution measuring apparatus Microtrac MT3100II (manufactured by Nikkiso Co., Ltd.). In lithium secondary batteries, a more satisfactory cycle characteristic tends to be obtained with a smaller average particle diameter of the active material particles 23.
  • the absolute amount of the volume expansion and shrinkage of the active material particles 23 accompanying the occlusion/release of lithium in the charge-discharge reaction of a lithium secondary battery or the like becomes small. Therefore, the absolute amount of distortion between the active material particles 23 in the negative electrode 200 during the charge-discharge reaction also becomes small.
  • silicon (Si) particles, silicon oxide (SiO) particles, silicon alloy particles, metal particles of tin (Sn), lead (Pb), aluminum (Al), or zinc (Zn), and particles of oxides of these metals can be used as the active material particles 23.
  • the active material particles 23 may also include particles made of a material alloyed with lithium. Examples of such materials include germanium, tin, lead, zinc, magnesium, sodium, aluminum, gallium, indium, and alloys thereof.
  • an arc melting method for example, an arc melting method, a liquid quenching method, a mechanical alloying method, a sputtering method, a chemical vapor deposition method, and a calcining method can be used.
  • a single roll quenching method, a twin roll quenching method, and various atomizing methods such as a gas atomizing method, a water atomizing method, and a disk atomizing method can be used as the liquid quenching method.
  • the active material particle 23 may be a core-shell type active material particle in which the abovementioned silicon (Si) particle, silicon oxide (SiO) particle, silicon alloy particle, tin (Sn) particle or the like is coated with a metal or the like.
  • the core-shell active material particles are produced by an electroless plating method, an electroplating method, a chemical reduction method, a vapor deposition method, a sputtering method, a chemical vapor deposition method, or the like. It is preferable that the shell portion be formed of the same metal as the metal forming the current collector 30. Bonding between the core-shell type active material particles and the current collector 30 is greatly improved, and excellent charge-discharge cycle characteristic can be obtained.
  • the shell portion may be formed of a silane coupling agent instead of the metal.
  • the active material particles 23 are subjected to surface treatment with a silane coupling agent, the active material particles 23 can be satisfactorily dispersed in the below-described slurry, and at the same time, binding property of the active material particles 23 to the polyimide layer 24 can be enhanced.
  • the polyimide layer 24 that coats the active material particles 23 is formed from a monomeric polyimide precursor. As a result, the polyimide layer 24 has a porous structure.
  • the porous structure as referred to herein, is a structure in which the polyimide layer 24 has a mesh-like structure and in which electrons and lithium ions can be smoothly transferred.
  • the active material particle 23 is not completely coated and it is possible to expose partially the surface of the active material particle 23. As a result, it is possible to prevent the coating of the polyimide layer 24 from interfering with the occlusion/release of lithium into/from the active material particles 23 in the charge-discharge reaction in the battery.
  • the thickness of the polyimide layer 24 is 0.5 nm or more and 50 nm or less, preferably 1 nm or more and 30 nm or less, and more preferably 3 nm or more and 15 nm or less.
  • the thickness of the polyimide layer is 0.5 nm or more and 50 nm or less, degradation of the active material due to charging and discharging can be suppressed, and transfer of electrons and lithium ions occurring between the active material and the electrolytic solution can be carried out smoothly, thereby making it possible to suppress capacity deterioration.
  • the polyimide resin contained in the polyimide layer 24 is a polymer resin including an imide bond in a repeating unit.
  • the polyimide resin contained in the polyimide layer 24 is formed from a monomeric polyimide precursor.
  • the molar ratio of the tetracarboxylic acid ester compound and the polyamine compound contained in the monomeric polyimide precursor solution (slurry) is usually in the range of 55 : 45 to 45 : 55.
  • the molar ratio of the tetracarboxylic acid ester compound and the polyamine compound can be appropriately changed to ratios other than those presented hereinabove, provided that the essence of the present invention is not affected.
  • the tetracarboxylic acid ester compound is preferably an aromatic tetracarboxylic acid ester compound. Further, the tetracarboxylic acid ester compound is preferably a tetracarboxylic acid diester compound.
  • the tetracarboxylic acid ester compound can be obtained very easily by esterifying the corresponding tetracarboxylic acid dianhydride with an alcohol. The esterification of the tetracarboxylic acid dianhydride is preferably carried out at a temperature of 50°C or higher and 150°C or lower.
  • alcohols for forming the tetracarboxylic acid ester compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, cyclohexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, phenol, 1-hydroxy-2-propanone, 4-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-hydroxy-2-butanone
  • Examples of other alcohols for forming the tetracarboxylic acid ester compound include polyhydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, glycerol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 1,2,6-hexanetriol, 2,2'-dihydroxydiethyl ether, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 3,6-dioxaoctane-1,8-diol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and dipropylene glycol. These alcohols may be used
  • tetracarboxylic acid ester compounds composed of the tetracarboxylic dianhydride and the alcohol
  • 3,3',4,4'-benzophenonetetracarboxylic acid diester (BTDA), pyromellitic dianhydride (PMDA), and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) are particularly preferable.
  • the tetracarboxylic acid ester compound can also be produced by another method, for example, by directly esterifying a tetracarboxylic acid.
  • trivalent amine compounds examples include 2,4,6-triaminopyrimidine (TAP), 1,3,5-triaminobenzene, 1,3,5-tris(4-aminophenyl)benzene, 3,4,4'-triaminodiphenyl ether, 6-phenylpteridine-2,4,7-triamine, tris(4-aminophenyl)methanol, melamine, 2',4',4-triaminobenzanilide, 2,5,6-triamino-3-methylpyrimidin-4(3H)-one, 1,4,5,8-tetraaminoanthraquinone, and 3,3'-diaminobenzidine.
  • TAP 2,4,6-triaminopyrimidine
  • 1,3,5-triaminobenzene 1,3,5-tris(4-aminophenyl)benzene
  • 3,4,4'-triaminodiphenyl ether 6-phenylpteridine-2,4,7-triamine
  • the polyamine compound may have an anionic group.
  • the anionic group for example, a carboxyl group, a sulfuric acid ester group, a sulfonic acid group, a phosphoric acid group, or a phosphoric acid ester group is used.
  • a carboxyl group is particularly preferable.
  • the polyamine compound having an anionic group for example, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid (3,5-DABA), or metaphenylenediamine-4-sulfonic acid is used.
  • a polyamine compound having an anionic group it is possible to form the polyimide layer 24 having an anionic group.
  • a polyamine compound having an anionic group and a polyamine compound not having an anionic group may be used in a mixture.
  • the polyamine compound having an anionic group preferably constitutes 30 mol% or more, more preferably 40 mol% or more, even more preferably 60 mol% or more, still more preferably 80 mol% or more, even more preferably 90 mol% or more, and still more preferably 95 mol% or more of the total polyamine compound.
  • metaphenylenediamine MPDA
  • 3,5-diaminobenzoic acid 3,5-DABA
  • 2,4,6-triaminopyrimidine TAP
  • the organic solvent dissolves the tetracarboxylic acid ester compound and the polyamine compound.
  • the organic solvent for example, alcohols for forming the abovementioned tetracarboxylic acid ester are preferably used. Specifically, lower alcohols such as methanol, ethanol, 1-propanol, and 2-propanol are preferably used as the alcohols.
  • lower alcohols such as methanol, ethanol, 1-propanol, and 2-propanol are preferably used as the alcohols.
  • N-methyl-2-pyrrolidone, dimethylacetamide, aromatic hydrocarbons or the like may be added to the organic solvent.
  • the monomeric polyimide precursor solution (slurry) may include an electrically conductive additive.
  • An example of the electrically conductive additive is an electrically conductive filler.
  • materials mentioned in the description of the active material layer can be used as the electrically conductive filler.
  • the amount of the polyimide layer 24 in the polyimide-coated active material particle 21 is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less of the total mass of the polyimide-coated active material particle 21.
  • the amount of the polyimide layer is 1% by mass or more and 50% by mass or less of the total mass of the polyimide-coated active material particle, deterioration of the active material due to charging and discharging can be prevented.
  • the amount of the polyimide layer is 1% by mass or more and 50% by mass or less of the total mass of the polyimide-coated active material particle, transfer of electrons and lithium ions occurring between the active material and the electrolytic solution can be carried out smoothly, thereby making it possible to suppress capacity deterioration.
  • the abovementioned polyimide-coated active material particles 21 are produced by a manufacturing method including a coating step of coating the active material particles 23 with a polyimide precursor solution including a monomeric polyimide precursor and a heating step of heating the active material particles 23 coated with the monomeric polyimide precursor.
  • a monomeric polyimide precursor solution (slurry) having the above composition is prepared, and the obtained slurry is applied to the entire surface of the active material particles 23.
  • a method (dipping method) in which the active material particles 23 are dipped in the slurry and then pulled up, and a method in which a fluidized bed apparatus is used and the slurry is sprayed while the active material particles are caused to flow in the apparatus can be used as a method for applying the slurry to the active material particles 23, but these examples are not limiting.
  • the active material particles 23 coated with the slurry are then heated.
  • the slurry covering the surface of the active material particles 23 is heated to cause an imidization reaction of the polyimide precursor, and a polyimide layer 24 having a thickness, for example, of 3 nm or more and 15 nm or less is formed.
  • the slurry for an electrode material includes at least the above-described polyimide-coated active material particles 21 and the aqueous binder 22.
  • the aqueous binder 22 those exemplified above in the description of the active material layer 20 can be used.
  • the aqueous binder 22 is contained in a state of being dissolved or dispersed in a water-soluble solvent such as water.
  • the slurry for an electrode material may further include an electrically conductive additive.
  • An example of the electrically conductive additive is an electrically conductive filler.
  • materials mentioned in the description of the active material layer can be used as the electrically conductive filler.
  • the slurry for an electrode material may include a dispersant or the like.
  • the dispersant added to the slurry for an electrode material uniformly disperses the polyimide-coated active material particles 21 in the slurry.
  • sorbitan monooleate, N,N-lauryldimethylamine, N,N-dimethylstearylamine, and N-cocoalkyl-1,3-diaminopropane are used as the dispersant. These dispersants may be used singly or in combination.
  • the current collector 30 to which the slurry for an electrode material has been applied is dried at a temperature of, for example, 80°C or more and 180°C or less.
  • aqueous binder is used as the binder in the electrode (negative electrode 200) produced by the above method, a water-soluble solvent can be used as a solvent contained in the binder. This eliminates the need to prepare a binder by using an organic solvent producing a relatively large load on environment. Further, the amount of the organic solvent used for electrode production can be reduced.
  • the heating temperature in the drying step can be lower than that when a polyimide is used as a binder.
  • the following method can be used to verify that the aqueous binder and polyimide-coated active material particles are included in the above-described negative electrode according to the present embodiment.
  • an electrolyte medium is removed by cleaning from the sheet-shaped negative electrode including the current collector. Then, the sheet electrode is immersed in an organic solvent such as chloroform. At this time, in the sheet electrode using the aqueous binder, the aqueous binder is extracted into the organic solvent, and the polyimide-coated active material particles and the current collector remain in the organic solvent. Removing the current collector remaining in the organic solvent and then filtering the organic solvent leaves a powdery residue. This powdery residue is presumed to be polyimide-coated active material particles.
  • the polyimide resin is not dissolved in chloroform and does not become powdery. Therefore, it is possible to discriminate between a negative electrode using a polyimide resin as a binder and the negative electrode of the present invention.
  • gas chromatographic mass analysis (pyrolytic GC/MC) is performed on the obtained powdery residue, for example, at a temperature of about 600°C, and the composition of the product is verified. This makes it possible to detect whether the polyimide is present in the residue.
  • FIG. 2 shows a cross-sectional configuration of a lithium secondary battery 1 (simply referred to hereinbelow as battery 1) of the present embodiment.
  • the battery 1 includes a positive electrode 100, a negative electrode 200, and a separator 300 disposed between the positive electrode 100 and the negative electrode 200.
  • an electrolyte-containing medium is filled between the positive electrode 100 and the negative electrode 200.
  • the positive electrode 100, the negative electrode 200, and the separator 300 are covered with a packaging material (not shown in the figure).
  • a known positive electrode for a lithium secondary battery is used for the positive electrode 100.
  • the positive electrode 100 includes an active material layer 120 and a current collector 130.
  • the active material layer 120 is formed on the current collector 130.
  • the active material layer 120 may have the same configuration as that of the active material layer 20 of the above-described negative electrode 200, except that the material of the active material particles is appropriately changed.
  • a lithium-containing transition metal oxide such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), and lithium manganese oxide (LiMn 2 O 4 ) can be used for the active material particles of the positive electrode 100.
  • a known separator for a lithium secondary battery is used for the separator 300.
  • a separator made of a polyimide resin, a glass nonwoven fabric separator, a pulp separator, an aramid separator, a separator made of a polypropylene resin, or a separator made of a polyamide imide resin is used.
  • the amount ratio (mass ratio) of the polymeric polyimide precursor to the monomeric polyimide precursor may be 0% or more and 70% or less, preferably 0% or more and 50% or less, and more preferably 0% or more and 30% or less.
  • the negative electrode includes a current collector and an active material layer including negative electrode active material particles and an aqueous binder.
  • the current collector can have the same configuration as the above-described current collector 30.
  • the aqueous binder included in the active material layer can have the same configuration as the above-mentioned aqueous binder 22.
  • the negative electrode active material particles included in the active material layer are not necessarily provided with the polyimide layer 24.
  • a charge-discharge rate and a cut-off voltage are set to predetermined values, charge-discharge cycles are performed a predetermined number of times, for example about 20 times, and a discharge capacity (mAh/g) is measured for every cycle. Then, for example, the ratio of the discharge capacity in the 20th cycle to the discharge capacity in the first cycle is calculated as a retention rate (%) representing an index of the charge-discharge cycle characteristic of the battery.
  • the charge-discharge rate in the charge-discharge cycle test can be, for example, 0.1C or 0.2C.
  • the charge-discharge cycle test of a battery using a polyimide as a binder and serving as a reference of the ratio of charge-discharge cycle characteristics for the battery of the present invention is performed under the same conditions as the charge-discharge cycle test of the battery of the present invention.
  • the retention rate (%) of the Reference Example 1-1 measured at the charge-discharge rate of 0.1C is used as the reference value of the retention rate (%). Further, when the charge-discharge rate is set to 0.2C, the retention rate (%) of Reference Example 1-2 measured at a charge-discharge rate of 0.1C is used as the reference value of retention rate (%).
  • the ratio of the cycle characteristic of the battery of the present invention to the reference value may be 43.0% or more, preferably 45.0% or more, more preferably 47.0% or more, yet more preferably 49.0% or more, and most preferably 51.0% or more. Further, when the charge-discharge rate of the charge-discharge cycle test is 0.2C, the ratio of the cycle characteristic of the battery of the present invention to the reference value also may be 43.0% or more, preferably 45.0% or more, more preferably 47.0% or more, yet more preferably 49.0% or more, and most preferably 51.0% or more.
  • a monomeric polyimide precursor solution was then prepared by cooling the BTDA diester solution to 45°C or less, and then adding 12.8 g (0.118 mol) of metaphenylenediamine (MPDA) (manufactured by Tokyo Chemical Industry Co., Ltd.) to the BTDA diester solution and stirring for 1 h while heating again to 50°C.
  • MPDA metaphenylenediamine
  • the obtained intermediate of polyimide-coated active material particles was thermally treated (calcined) for 3 h at 350°C and sintered to obtain polyimide-coated active material particles.
  • the solid fraction ratio (% by mass) of each material in the finally obtained polyimide-coated active material particles is shown in Table 2.
  • a total of 0.308 g of the above-described polyimide-coated active material particles, 0.011 g of Ketjen black (manufactured by Lion Corporation) and 0.34 g of water were added to 0.1 g of an aqueous sodium polyacrylate solution (product name: Aqualic (registered trademark), product number: DL 453, molecular weight: 50,000, manufactured by Nippon Shokubai Co., Ltd.), followed by thorough mixing with a mortar to prepare a slurry for a negative electrode material.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Example 1-1 is as shown in Table 2.
  • This slurry for a negative electrode material was applied to one side of a rolled copper foil (thickness 40 ⁇ m) as a current collector so that the thickness after drying was 17 ⁇ m, and then dried to prepare a negative electrode intermediate.
  • the negative electrode intermediate was cut into a circular shape having a diameter ( ⁇ ) of 11 mm and dried for 2 h at 100°C under vacuum to prepare a negative electrode.
  • the solid fraction ratio (% by mass) of each material in the finally obtained negative electrode is shown in Table 3.
  • a nonaqueous electrolytic solution in which LiPF 6 was dissolved to a LiPF 6 concentration of 1 mol/L in a solvent prepared by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 1 : 1 was used.
  • a lithium ion secondary battery was fabricated by incorporating the negative electrode, the counter electrode and the nonaqueous electrolytic solution prepared as described above into a CR2032-type coin cell made of SUS.
  • the positive electrode and the counter electrode were disposed so as to face each other, with a polypropylene separator (thickness: 25 ⁇ m) being interposed therebetween.
  • the separator was reinforced with a glass fiber cloth.
  • the lithium secondary battery obtained as described above was subjected to a charge-discharge cycle test.
  • the ambient temperature was set to 25°C
  • the charge-discharge rate was set to 0.1C
  • the cutoff voltage was 0.0 V at the time of charging and 1.5 V at the time of discharging
  • the charge-discharge cycle was performed 20 times.
  • the discharge capacity (mAh/g) was measured for each cycle.
  • "the ratio of the discharge capacity in the 20th cycle to the discharge capacity in the first cycle” was determined as the retention rate (%).
  • the retention rate (%) of the lithium secondary battery obtained in the below-described Example 1-8 is set as a reference value (that is, 1), and the retention rate (%) thus obtained is expressed as a relative ratio of the retention rate to the reference value.
  • Example 1-2 the amount of the electrically conductive additive (Ketjen black and VGCF) added to the polyimide precursor solution (slurry) for coating was twice that of Example 1-1.
  • 2.48 g of Ketjen black (manufactured by Lion Corporation) having a primary particle diameter of 34 nm and 0.62 g of vapor-grown carbon fibers (VGCF) (manufactured by Showa Denko K.K.) were added to 10 g of the monomeric polyimide precursor solution to prepare a polyimide precursor solution (slurry) for coating. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. Further, as shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Example 1-2 to the retention rate of the lithium secondary battery of Example 1-8 was 0.855.
  • Example 1-3 the amount of the polyimide precursor solution (slurry) for coating the active material particles was 1.66 times that of Example 1-1.
  • a total of 1.37 g of Ketjen black (KB) (manufactured by Lion Corporation) having a primary particle diameter of 34 nm, 0.34 g of vapor-grown carbon fibers (VGCF) (manufactured by Showa Denko K.K.), and 40 g of N-methyl-2-pyrrolidone were added to 16.6 g of the monomeric polyimide precursor solution to obtain a polyimide precursor solution (slurry) for coating.
  • Example 1-1 A total of 24.8 g of silicon powder (product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS) having a median diameter of 2.13 ⁇ m was added to the slurry. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • silicon powder product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. Further, as shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Example 1-3 to the retention rate of the lithium secondary battery of Example 1-8 was 1.049.
  • Example 1-4 a carbon powder (purity 98.8%) (manufactured by Ito Graphite Co., Ltd.) was used as active material particles in addition to the silicon powder used in Example 1-1.
  • the mass ratio of the silicon powder and the carbon powder was 30 : 70.
  • Coating with the polyimide precursor solution (slurry) was performed only on the silicon powder.
  • a mixture of styrene butadiene rubber (SBR) and carboxymethyl cellulose (CMC) was used instead of the sodium polyacrylate of Example 1-1 as an aqueous binder used for preparing the negative electrode.
  • the mass ratio of SBR and CMC was 3 : 2.
  • Example 1-4 no electrically conductive additive was added to the negative electrode material slurry.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Example 1-4 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1. Then, the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1, except that the charge-discharge rate was set to 0.2C.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. Further, as shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Example 1-4 to the retention rate of the lithium secondary battery of Example 1-7 was 0.963.
  • Example 1-5 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-5 to the retention rate of the lithium secondary battery of Example 1-7 was 1.051.
  • Example 1-6 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1, except that the charge-discharge rate was set to 0.2C.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-6 to the retention rate of the lithium secondary battery of Example 1-7 was 0.884.
  • Example 1-7 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • commercially available sodium polyacrylate product name: Aqualic (registered trademark), product number: DL522, molecular weight: 170,000, manufactured by Nippon Shokubai Co., Ltd.
  • sodium polyacrylate molecular weight: 50,000
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the retention rate of the lithium secondary battery measured in Example 1-7 was taken as a reference value (that is, 1.000) for evaluating the retention rate of the lithium secondary batteries in other Examples, Comparative Examples, and the like.
  • Example 1-8 carboxymethyl cellulose (CMC) was used instead of the sodium polyacrylate of Example 1-1 as an aqueous binder used for fabricating the negative electrode. Further, in Example 1-8, the amounts of the aqueous binder (CMC) and Ketjen black used for fabricating the negative electrode were changed.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Example 1-8 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Example 1-8 to the retention rate of the lithium secondary battery of Example 1-7 was 0.465.
  • Example 1-9 3,5-diaminobenzoic acid (3,5-DABA) was used instead of metaphenylenediamine (MPDA) of Example 1-1 as the diamine compound included in the monomeric polyimide precursor solution.
  • a BTDA diester solution was prepared by loading 18.4 g (0.057 mol) of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) (manufactured by Daicel Chemical Industries, Ltd.), 6.30 g (0.140 mol) of ethanol (manufactured by Ueno Chemical Industries Ltd.), and 66.65 g of N-methyl-2-pyrrolidone so that the solid fraction of the polyimide precursor solution was 27.0%, and then stirring the contents of the synthesis vessel for 1 h while heating at 90°C.
  • BTDA 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride
  • ethanol manufactured by Ueno Chemical Industries Ltd.
  • Example 1-9 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • commercially available sodium polyacrylate product name: Aqualic (registered trademark), product number: DL522, molecular weight: 170,000, manufactured by Nippon Shokubai Co., Ltd.
  • sodium polyacrylate molecular weight: 50,000
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-9 to the retention rate of the lithium secondary battery of Example 1-7 was 0.925.
  • Example 1-10 2,4,6-triaminopyrimidine (TAP) was used instead of metaphenylenediamine (MPDA) of Example 1-1 as the polyamine compound included in the monomeric polyimide precursor solution.
  • a BTDA diester solution was prepared by loading 35.7 g (0.111 mol) of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) (manufactured by Daicel Chemical Industries, Ltd.), 10.22 g (0.22 mol) of ethanol (manufactured by Ueno Chemical Industries Ltd.), and 44.78 g of N-methyl-2-pyrrolidone so that the solid fraction of the polyimide precursor solution was 45.0%, and then stirring the contents of the synthesis vessel for 1 h while heating at 90°C.
  • BTDA 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride
  • ethanol manufactured by Ueno Chemical Industries Ltd.
  • Example 1-10 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • commercially available sodium polyacrylate product name: Aqualic (registered trademark), product number: DL522, molecular weight: 170,000, manufactured by Nippon Shokubai Co., Ltd.
  • sodium polyacrylate molecular weight: 50,000
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-10 to the retention rate of the lithium secondary battery of Example 1-7 was 1.106.
  • Example 1-11 a polymeric polyimide precursor was added to the monomeric polyimide precursor solution. More specifically, a polyamic acid obtained by polymerizing BTDA and MPDA as raw materials was used. The mass ratio of the monomeric polyimide precursor and the polymeric polyimide precursor contained in the polyimide precursor solution (slurry) for coating was 75 : 25. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-11 to the retention rate of the lithium secondary battery of Example 1-7 was 0.613.
  • Example 1-12 a polymeric polyimide precursor was added to the monomeric polyimide precursor solution. More specifically, a polyamic acid obtained by polymerizing BTDA and MPDA as raw materials was used. The mass ratio of the monomeric polyimide precursor and the polymeric polyimide precursor contained in the polyimide precursor solution (slurry) for coating was 50 : 50. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material obtained in this Example is shown in Table 2.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3.
  • the relative ratio of the retention rate of the lithium secondary battery of Example 1-12 to the retention rate of the lithium secondary battery of Example 1-7 was 0.562.
  • Example 1-13 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder as the active material particles.
  • a carbon powder purity 98.8% (manufactured by Ito Graphite Co., Ltd.) was also used. The mass ratio of the silicon oxide powder and the carbon powder was 30 : 70. Coating with the polyimide precursor solution (slurry) was performed only on the silicon oxide powder.
  • Carboxymethyl cellulose (CMC) was used instead of the sodium polyacrylate of Example 1-1 as an aqueous binder used for fabricating the negative electrode.
  • Example 1-13 the amounts of the aqueous binder (CMC) and Ketjen black used for fabricating the negative electrode were changed.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Example 1-13 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Example 1-13 to the retention rate of the lithium secondary battery of Example 1-7 was 1.034.
  • Comparative Example 1-1 a negative electrode was fabricated by using active material particles not coated with a polyimide instead of the polyimide-coated active material particle produced in Example 1-1.
  • the active material particles used were a silicon powder (product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS) having a median diameter of 2.13 ⁇ m.
  • the amount of Ketjen black used for fabricating the negative electrode was changed.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-1 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-1 to the retention rate of the lithium secondary battery of Example 1-7 was 0.089.
  • a negative electrode was fabricated by using active material particles not coated with a polyimide instead of the polyimide-coated active material particle produced in Example 1-4.
  • the active material particles used were a silicon powder (product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS) having a median diameter of 2.13 ⁇ m.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-2 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-4, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1, except that the charge-discharge rate was 0.2C.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-2 to the retention rate of the lithium secondary battery of Example 1-7 was 0.014.
  • Comparative Example 1-3 a silicon oxide (SiO) powder was used instead of the silicon powder which was used in in Comparative Example 1-1 and was not coated with a polyimide.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-3 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Comparative Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-3 to the retention rate of the lithium secondary battery of Example 1-7 was 0.246.
  • Comparative Example 1-4 a negative electrode was fabricated by using active material particles not coated with a polyimide instead of the polyimide-coated active material particles produced in Example 1-8.
  • the active material particles used were a silicon powder (product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS) having a median diameter of 2.13 ⁇ m.
  • the amount of Ketjen black used for fabricating the negative electrode was changed.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-4 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-4 to the retention rate of the lithium secondary battery of Example 1-7 was 0.065.
  • Comparative Example 1-5 a negative electrode was fabricated using polyimide-coated active material particles which were coated with a polymeric polyimide precursor solution instead of the polyimide-coated active material particles produced in Example 1-1.
  • the active material particles were coated only with the polymeric polyimide precursor solution, without including the monomeric polyimide precursor in the coating.
  • a polymeric polyimide precursor solution including a polyamic acid obtained by polymerizing BTDA and MPDA as raw materials was prepared.
  • Polyimide-coated active material particles were prepared using the polymeric polyimide precursor solution.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-5 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-5 to the retention rate of the lithium secondary battery of Example 1-7 was 0.460.
  • a negative electrode was fabricated using polyimide-coated active material particles coated with a polymeric polyimide precursor solution in the same manner as in Comparative Example 1-5. Specifically, a monomeric polyimide precursor solution including a polyamic acid obtained by polymerizing PMDA and ODA as raw materials was prepared. Polyimide-coated active material particles were prepared using the monomeric polyimide precursor solution. The solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-6 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-6 to the retention rate of the lithium secondary battery of Example 1-7 was 0.136.
  • Comparative Example 1-7 a negative electrode was fabricated using active material particles coated with carbon instead of active material particles not coated with a polyimide coating which were used in Comparative Example 1-1.
  • a silicon oxide (SiO) powder manufactured by Osaka Titanium Technologies Co., Ltd, product name: CC Powder
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Comparative Example 1-7 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Comparative Example 1-7 to the retention rate of the lithium secondary battery of Example 1-7 was 0.079.
  • Described below are reference examples using a water-insoluble polyimide resin as a binder which is a material of the negative electrode.
  • a negative electrode was fabricated using active material particles not coated with a polyimide instead of the polyimide-coated active material particles produced in Example 1-1.
  • the active material particles used were a silicon powder (product name: Silgrain (registered trademark) e-Si, manufactured by Elkem AS) having a median diameter of 2.13 ⁇ m.
  • Example 1-1 a monomeric polyimide precursor solution was prepared in the same manner as in "1. Preparation of Monomeric Polyimide Precursor Solution" in Example 1-1. Then, 1.86 g of the above-mentioned active material particles, 0.093 g of Ketjen black (manufactured by Lion Corporation) and 0.023 g of vapor-grown carbon fibers (VGCF) (manufactured by Showa Denko K.K.) were added to 1 g of the obtained monomeric polyimide precursor solution to prepare a slurry for a negative electrode material.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Reference Example 1-1 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Example 1-1, and the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Reference Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Reference Example 1-1 to the retention rate of the lithium secondary battery of Example 1-7 was 1.079.
  • Reference Example 1-2 a silicon oxide (SiO) powder (product name: BP Powder, manufactured by Osaka Titanium Technologies Co., Ltd.) having a median diameter of 5.2 ⁇ m was used instead of the silicon powder not coated with a polyimide which was used in Reference Example 1-1.
  • the solid fraction ratio (% by mass) of each composition in the slurry for a negative electrode material used in Reference Example 1-2 is as shown in Table 2. Except for this, a battery was fabricated in the same manner as in Reference Example 1-1. Then, the charge-discharge cycle characteristic of the battery was measured in the same manner as in Example 1-1, except that the charge-discharge rate was 0.2C.
  • the solid fraction ratio (% by mass) of each material in the polyimide-coated active material particles obtained in this Reference Example is shown in Table 2. Further, the solid fraction ratio (% by mass) of each material in the negative electrode obtained in this Example is shown in Table 3. As shown in Table 3, the relative ratio of the retention rate of the lithium secondary battery of Reference Example 1-1 to the retention rate of the lithium secondary battery of Example 1-7 was 1.455.
  • Example No. Types of materials Active material Coating on active material particles Binder in electrode material Example 1-1 Si BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL453) Example 1-2 Si BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL453) Example 1-3 Si BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL453) Example 1-4 Si + C BTDA/m-PDA (monomeric) SBR + CMC Example 1-5 SiO BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL453) Example 1-6 SiO BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL453) Example 1-7 SiO BTDA/m-PDA (monomeric) Sodium polyacrylate (product number: DL522)
  • Example 1-1 69.60 7.35 23.05 13.05 10.00 0 0 0.1C 0.804
  • Example 1-2 65.25 11.70 23.05 13.05 10.00 0 0 0.1C 0.855
  • Example 1-3 63.08 7.35 29.58 20.48 9.10 0 0 0.1C 1.049
  • Example 1-5 69.60 7.35 23.05 13.05 10.00 0 0 0.1C 1.051
  • Example 1-6 69.60 7.35 23.05 13.05 10.00 0 0 0.2C 0.884
  • Example 1-7 69.60 7.35 23.05 13.05 10.00 0 0 0.2C 1.000
  • Example 1-8 50.40 20.15 29
  • the ratio of retention rates was then determined with reference to the retention rate (%) of a battery equipped with a negative electrode having an active material layer using a polyimide as a binder on the basis of the results on the charge-discharge cycle characteristics measured in the above-mentioned Examples and Comparative Examples.
  • the results of Reference Example 1-1 and Reference Example 1-2 were used as retention rates of batteries taken as a reference.
  • the ratio of charge-discharge cycle characteristics was calculated using the retention rate (%) of Reference Example 1-1 as a reference value.
  • the ratio of the charge-discharge cycle characteristics in the Examples was 43.0% or more with respect to the reference value.
  • the ratio of the charge-discharge cycle characteristics in the Comparative Examples was less than 43.0% with respect to the reference value.
  • Example 2 the polyimide-coated active material particles prepared in the above-described Examples 1-1 and 1-12 and Comparative Example 1-5 were subjected to Auger electron spectroscopic analysis to confirm the surface state of the particles.
  • Auger electron spectroscopic analysis an Auger spectroscopic apparatus PHI-700 (manufactured by ULVAC-PHI, Inc.) was used.
  • the analysis conditions were as follows.
  • Fig. 3 shows the analysis results relating to the polyimide-coated active material particle of Example 1-1.
  • Fig. 3(a) is a graph showing the results of depth analysis of the particle.
  • Fig. 3(b) is an image obtained by photographing the state of the particle.
  • Fig. 4 shows the analysis results relating to the polyimide-coated active material particle of Example 1-12.
  • Fig. 4(a) is a graph showing the results of depth analysis of the particle.
  • Fig. 4(b) is an image obtained by photographing the state of the particle.
  • Fig. 5 shows the analysis results relating to the polyimide-coated active material particle of Comparative Example 1-5.
  • Fig. 5(a) is a graph showing the results of depth analysis of the particle.
  • Fig. 5(b) is an image obtained by photographing the state of the particle.
  • the depth at which the concentration change of each component does not occur is apparently the thickness of the polyimide layer covering the active material particle. From the results shown in the figures, it is assumed that the thickness of the polyimide layer increased as the amount of the monomeric-derived component in the coating increased. Also, from the graphs of Figs. 3 (a) and 4(a) , it was found that the C component was present at a constant concentration even after the concentration of the Si component stopped changing. It is conceivable from this result that where the active material particles are coated with a polyimide layer including a monomeric-derived component, the monomeric-derived component may enter fine gaps of the active material particles (Si) .

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EP3264504A4 (fr) 2018-10-31
CN107251281B (zh) 2021-03-02
WO2016136543A1 (fr) 2016-09-01
US10686187B2 (en) 2020-06-16
KR20170107083A (ko) 2017-09-22

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